Detergent compositions containing n-chloro-imides

ABSTRACT

DETERGENT COMPOSITION CONTAINING A WATER-SOLUBLE ORGANIC DETERGENT; AN N-HALO-IMIDE; AND AN AMOUNT EFFECTIVE TO STABILIZE SAID N-HALO-IMIDE OF ANHYDROUS SODIUM ACETATE. THE DETERGENT COMPOSITIONS EXHIBIT DESIRABLE CLEANING, OXIDIZING AND BLEACHING PROPERTIES AND ARE STABILIZED AGAINST LOSS OF AVAILABLE HALOGEN.

United States Patent O Int. Cl. Clld 7/54 US. Cl. 252-95 13 ClaimsABSTRACT OF THE DISCLOSURE Deteregnt compositions containing awater-soluble organic detergent; an N-halo-imide; and an amounteffective to stabilize said N-halo-imide of anhydrous sodium acetate.The detergent compositions exhibit desirable cleaning, oxidizing andbleaching properties and are stabilized against loss of availablehalogen.

BACKGROUND OF THE INVENTION This invention relates to detergentcompositions containing a detergent component and a source of availablehalogen and which are adapted to provide in use both cleansing andoxidizing functions. More particularly, it relates to detergentcompositions containing, as a bleaching agent, a source of halogen and astabilizing compound effective to stabilize the bleaching agent againstloss of its available halogen.

The use of bleaching agents in detergent compositions adapted to theprovision of cleansing, oxidizing, bleaching and disinfecting propertieshas been well known in the art. For example, the utilization ofchlorine-, bromineand oxygen-containing bleaching compounds has beendescribed in US. Pats. 3,048,546- to Lake et a1. (August 7, 1962);3,556,711 to Stalter (Jan. 19, 1971); 3,583,922 to McClain et a1. (June8, 1971); 3,575,865 to Burke et a1. (Apr. 20, 197 1) and 3,578,598 toBurke (May 11, 1971).

Hypohalite-releasing bleaching agents, i.e., those which liberatehypohalite, e.g. hypochlorite, upon contact With Water comprise arelatively preferred class of bleaching agents employed in the detergentarts. These hypohalitereleasing agents include those of theN-halo-imide-type and are especially adapted to the provision ofrelatively high levels of oxidizing and bleaching performance. While theN-halo-imides are effective to provide desirable bleaching and oxidizingproperties, such materials tend upon storage to lose their bleaching andoxidizing potential. The loss of available chlorine or bromine isparticularly notable upon storage under adverse conditions oftemperature and humidity. Inasmuch as the N-halo-imides are adapted toprovide their available halogen upon contact with water, as for example,during a cleansing operation, they are particularly susceptible to lossof available halogen by reason of contact with levels of moisture whichmight be encountered during storage, particularly under adverseconditions of temperature and humidity. Thus it is found that theoxidizing and bleaching capacity of an N-halo-imide bleaching compoundin a detergent composition can diminish rather markedly over relativelyshort periods of storage, for example, over periods of time as short asone or two days under particularly adverse conditions of temperature andhumidity.

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The present invention resides in detergent compositions having aWater-soluble organic detergent cOmponent, an N-halo-imide bleachingagent as a source of available halogen and an eifective amount of astabilizing agent cap-able of minimizing the loss of available halogenupon storage. In accordance with the present invention, it has beendiscovered that there can be prepared detergent compositions exhibitingboth desirable cleansing and oxidizing properties even after storageunder relatively severe conditions of temperature and humidity.

SUMMARY OF THE INVENTION The present invention is based in part upon thediscovery that the incorporation of anhydrous sodium acetate in adetergent composition containing an N-halo-imide bleaching agent permitsthe preparation of detergent compositions exhibiting desirable cleansingand oxidizing effects and having an improved tendency to effectivelyreduce halogen loss for relatively extended periods of time.Accordingly, in its composition aspect, the present invention provides adetergent composition stabilized against loss of available halogen andconsisting essentially of a water-soluble organic detergent; anN-halo-im'ide bleaching agent capable of liberating hypohalite uponcontact with aqueous media; and anhydrous sodium acetate in an amountsufiicient to stabilize the N-halo-imide against loss of halogen.

It has been discovered that detergent compositions containing anN-halo-imide bleaching agent can be effectively stabilized against lossof available halogen so as to maximize in use the desirable bleachingand oxidizing properties which normally characterize such agents.

DETAILED DESCRIPTION OF THE INVENTION The water-soluble organicdetergents which can be used in the detergent compositions of thisinvention are anionic, nonionic, zwitterionic and cationic organicdetergents.

Examples of suitable deteregnts for use in the compositions of thisinvention include thoese detergents described in US. Pat. 3,318,817 atcolumn 4, line 37, through column 6, line 30, and column 9, line 6through line 57. This list is merely illustrative. The disclosure ofthis patent is incorporated herein by reference.

Suitable cationic detergents are those having the formula R-N (-R Xwherein R is an alkyl chain containing from about 8 to about 20 carbonatoms, each R is selected from the group consisting of alkyl and alkanolgroups containing from 1 to 4 carbon atoms and benzyl groups there beingnormally no more than one benzyl group and two R groups can be joined byeither a carbon-carbon ether, or imino linkage to form a ring structure,and X represents a halogen atom, sulfate group, nitrate group or otherpseudohalogen group. Specific examples are coconut alkyl trimethyl aminechloride, dodecyl dimethyl benzyl bromide, and dodecyl methyl morpholinochloride.

While suitable detergent compounds of the invention include soap,non-soap anionic, nonionic, zwitterionic, and cationic detergents ashereinbefore mentioned, preferred herein are the non-soap anionicdetergents. Examples of these preferred anionic detergents are thewater-soluble sulfated and sulfonated synthetic detergents. Moreparticularly, it is preferred to employ an alkyl benzene sulfonatedetergent wherein the alkyl group has from 8 to 18 carbon atoms.Suitable examples are sodium decyl benzene sulfonate, sodium dodecyl andpentadecyl sulfonates wherein the dodecyl and pentadecyl groups arederived from a propylene polymer, and sodium octadecyl benzenesulfonates. Other preferred anionic detergents are the surface-activesulfated or sulfonated aliphatic compounds, preferably having 8 to 22carbon atoms. Examples thereof are the long-chain pure or mixed higheralkyl sulfates, e.g., lauryl sulfate and coconut fatty alcohol sulfate.

The anionic detergent components are commonly used in the form of theirwater-soluble salts. Preferred watersoluble cations are the alkali metaland ammonia cations, the sodium and potassium cations being particularlypreferred.

The purpose of the organic detergent component is to provide its knownand principal detergency or cleansing effects. The amount of detergentemployed in the compositions of the invention will vary depending uponthe particular soiling situation encountered, the nature of thedetergent employed, the particular type of composition prepared, e.g.,laundry pre-soak composition, heavy-duty laundry detergent composition,automatic dishwashing composition, abrasive scouring composition or thelike. Generally, the compositions of the invention contain the detergentcomponent in an amount of from 0.1% to 60%, the lower limit being basedon the detergency requirement and the upper limit on such considerationsas streaking, rinsing, sudsing and the like. In the case of preferredabrasive scouring compositions, described in greater detail hereinafter,the detergent component is employed in an amount of from 0.1% to byweight of the cleanser composition. Preferably, the detergent componentis present in such compositions in an amount of from 1% to 4% by weight.

The N-halo-imide bleaching and oxidizing agents employed herein areheterocyclic imides having from 4 to about 6 members in the ring, andare characterized by the following structure where X is halogen (e.g.chlorine or bromine) and in which the electron-donating nitrogen atom isdoubly activated to an acidic state by virtue of its proximity to twoelectropositive carbonyl groups. Suitable N-halo-imide compounds are theN-chloro-derivatives of cyanuric acid such as mono-, diandtrichlorocyanuric acid. Other examples include the N-chlorosuccinimides, N-chloro-malonirnides, N-chloro phthalimides and N-chloronaphthalimides. Other examples are described in U.S. Pat. 3,406,- 116 toVitale (Oct. 15, 1968) and in U.S. Pat. 3,257,324 to Wearn et al. (June21, 1966). These N-chloroimides can be employed as a single bleachingsource or in com bination with an alkali metal, e.g. sodium bromide forprovision of a hypobromite species.

Suitable N-bromo-imides include hypobromite-liberating compounds such astribrornocyanuric acid, dibromocyanuric acid, potassiumdibromocyanurate, N-bromosuccinimide, N-bromomalonimide, and 1,3dibromo-5,5-dimethylhydantoin. N-halo-imides which yield bothhypochlorite and hypobromite in solution such as N-dibromo-N-moonchloro-cyanuric acid and potassiumN-monobromo-N-monochlorocyanurate can also be employed. Examples ofthese compounds are described in U.S. Pat. 3,575,865 to Burke et al.

Certain of the N-halo-imide compounds herein are capable of saltformation and the alkali and alkaline earth metal salts thereof areuseful herein. As used herein, the term N-halo-imide is intended asembracing the N-haloimides per se and the various salts thereof,notwithstanding that some of the N-halo-imides are not capable of saltformation. Especially preferred salts herein by reason of theirdesirable bleaching eflicacy, inherent stability in relation to otherN-halo-imide compounds and odor characteristics are the alkali metal,e.g., potassium and sodium, dichloroisocyanurates.

The N-halo-imide compound of the compositions of the invention can beemployed in an amount which varies over a wide range. The particularamount employed will deend on the nature of the cleaning problempresented and the type of composition formulated. Generally, theemployment of an amount in the range of from 0.1 to 95% of the detergentcomposition will be sufficient to provide a level of oxidizing orbleaching power so as to make possible eificient cleansing, oxidizingand bleaching performance under the types of cleaning situationsnormally encountered in house o erations.

It will be appreciated that certain types of detergent formulations willcontain more or less of the bleaching or oxidizing component thanothers. Compositions formulated for fabric treatment, e.g., pre-soakingcompositions, laundry bleach-additive compositions and heavy-dutylaundry detergents, will contain from 0.1% to 95% and preferably from10% to 90% by weight of the composition. Abrasive scouring compositionswill contain from about about 0.1% to 25% and preferably from 0.2 to 2%of the N-halo-imide compound.

The N-halo-imide bleaching agents of the invention are preferablyprovided in a particulate form and in a substantially dry state, i.e.,free of uncombined water. Uncombined water is referred to herein ascontemplating moisture content other than that which is combined withthe bleaching agent as water of hydration or crystallization. Preferablythe N-halo-imide compound is employed in a particulate form that permitsready solubilization in an aqueous solution or slurry and which makespossible ready mixing of the N-halo-imide with detergent granules,builder salts and like components conventionally employed in thedetergent arts. The N-halo-imide component is preferably sized as topermit passage of a major portion, e.g., to 90%, through a mesh (Tyler)screen.

The sodium acetate stabilizing compound, which in combination with anorganic detergent and an N-haloimide bleaching agent, permits theprovision of cleaning compositions having bleaching and oxidizing power,is an anhydrous form of sodium acetate. The stabilizing agent, which iscommercially available and readily incorporated into detergentcompositions having an N-halo-imide bleaching compound, provides anexceptionally high degree of stabilization against halogen loss. Thecompositions of the invention are additionally characterized by reducedfilming and/or streaking properties when employed in the cleansing ofhard surfaces. Thus, procelain or ceramic surfaces treated, for example,by sponge-application of a detergent composition of the invention in theform of a solution or slurry exhibit a reduced tendency to filming andstreaking. The reduction is observed in the case of unrinsed surfaceswhere the solufion or slurry is merely rubbed across the hard surfaceand in the case of rinsed surfaces where the composition is rubbedacross the surface and rinsed by passing water over the cleansed surfacearea. The filming and streaking advantages of compositions of theinvention containing sodium acetate are in contrast to the relativelygreater levels of filming and streaking observed in the case of theemployment of similar detergent compositions which do not contain thesodium acetate of the invention. The reduced filming and streakingadvantages may be of particular significance in cleansing operationsWhere there is inadequate rilrgsing, e.g., in the rinsing of sinkfaucets, fixtures or the li e.

The anhydrous sodium acetate can be added to a detergent formulation inany of a number of convenient Ways. For example, granular or powderedsodium acetate can be dry-mixed with the organic detergent andN-haloimide compound so as to achieve a substantially uniformdistribution throughout the mixture. Alternatively, an aqueous solutionof the sodium acetate can be applied, as by spraying, to an organicdetergent, builder salt or other component commonly employed indetergent compositions and subsequently dried and admixed with theN-haloimide compound.

The amount of sodium acetate employed in the detergent compositions ofthe invention will vary depending upon storage conditions, the extent towhich the sodium acetate loses its hydration capacity or desiccantproperties upon storage, the amount of N-halo-imide bleaching agentpresent, the soiling problem encountered, the type of detergentformulation formulated, and the like. For example, compositionsformulated for use in the washing and bleaching of fabrics, which willnormally contain the lower amount of N-halo-imide compound as comparedwith compositions intended for other uses, will generally contain acorrespondingly reduced amount of the sodium acetate stabilizing agent.Other compositions adapted to soil-removal problems which may be moresevere, as might be encountered in the case of abrasive scouringcleanser compositions, will contain a relatively higher amount of sodiumacetate stabilizing agent to correspond to the relatively greater amountof N-halo-imide compound.

The conditions to which the compositions of the invention are subjectedin manufacture and storage will determine in part the amount ofanhydrous sodium acetate employed. Thus, compositions subjected inmanufacture or storage to conditions of high humidity will contain agreater level of sodium acetate than those manufactured and/or storedunder conditions of low humidity. The employment of an amount of sodiumacetate in relationship to the amount of free or loosely-bound moisturepermits the preparation of compositions which maximize storage stabilityunder the moisture conditions normally encountered in manufacture orstorage. An amount of sodium acetate corresponding to a ratio by weightof sodium acetate to such mosture in the composition of the invention of0.4:1 to 150:1 is suitably employed to provide against moisture effects.Preferably, a ratio from 2:1 to :1 is employed.

The compositions of the invention can be formulated for employment inmeeting the problems presented by the soiling and staining of a varietyof types of materials, including fabrics and hard surfaces, such asdishware, pots and pans, kitchen utensils, ceramic surfaces, such asenamel ware and the porcelain surfaces of laundry washtubs, kitchensinks, and the like. Thus, the comopsitions of the invention compriselaundry presoaking compositions for the removal of soils and stains fromfibrous materials, including fabrics, garments, household laundry, andthe like. Heavy-duty laundry detergent compositions and dishwashingcompositions are also contemplated as suitable formulations for theincorporation of N-halo-imide bleaching agent and sodium acetatestabilizer. In use, the stabilized compositions of the invention can beadded to water to provide an aqueous medium in the form of a solution orslurry for use in the treatment of the particular soiling situationencountered. The amount of the detergent composition employed will, ofcourse, depend on the nature of the cleaning problem presented and theamount of N- halo-imide bleaching agent employed in the composition.Thus, concentrated solutions will be employed in the treatment ofceramic surfaces where the possibility of damage to ceramic surfaces islow, while less concentrated solutions will be employed for thetreatment of textiles where the possibility of fabric damage will be ofgreater significance.

The detergent compositions of the present invention can contain avariety of ingredients in addition to those mentioned hereinbefore.Thus, alkaline detergency builders can be employed for enhanced cleaningeffects. These detergency builders enhance the detergency effect of theorganic detergent component and aid in the regulation of the desired pHof the detergent composition. Suitable alkaline detergency buildersinclude, for example, trisodium phosphate, tetrasodium pyrophosphate,sodium acid pyrophosphate, sodium tripolyphosphate, sodium monobasicphosphate, sodium dibasic phosphate, sodium hexametaposphate, sodiumcitrate, sodium silicates (SiO Na O of 1:1 to 3.2:1), sodium carbonate,borax, trisodium nitriloacetate and the like. Mixtures of two or moreinorganic or organic salts can be employed, as can mixtures of inorganicand organic salts. Other examples of suitable alkaline detergencybuilders include those described in U.S. Pat. 3,309,319 at column 4,line 44 through column 5, line 9. The disclosure of this patent isincorporated herein by reference.

Other ingredients which can also be present in the compositions of theinvention include inert inorganic salts such as sodium chloride, sodiumsulfate, potassium chloride and potassium sulfate, these being includedin the compositions in amounts less than about 20% by weight of thecomposition. Other minor ingredients which can be included areanti-caking agents such as hydrated magnesium trisilicate, sodiumcarboxymethylcellulose, sulfamic acid, perfume, antiseptics, germicides,aluminum-mark-removing agents such as calcium oxide or hydroxide,coloring agents and the like.

The compositions of the invention are prepared so as to be substantiallydry and free-flowing upon manufacture and during storage. Inasmuch asthe bleaching agents em loyed are moisture-sensitive and tend to losetheir oxidizing potential under adverse storage conditions, they shouldbe formulated so as to be substantially devoid of free or loosely-boundwa er. Accordingly, the compositions of the invention will contain lessthan about 5% moisture, eg. 0.1 to 5%, atthe time of manufacture,preferably from 0.1 to 1%. Storage conditions may. however, cause thecompositions to pick no additional moisture in which case thecompositions of the invention can contain from about 0.1% to about 10%moisture.

A preferred embodiment of the compositions of the invention comprisesabrasive scouring cleanser compositions. These compositions comprise awater-soluble organic or soap-like detergent material, a water-insolubleabrasive scouring material, an alkaline inorganic builder salt forcertain cleaning effects, particularly grease removal, an N-chloroimidebleaching agent and sodium acetate stabilizing agent. Preferred abrasivescouring cleanser compositions of the invention include those whichconsist essentially, by weight, of: (1) from 0.1% to 10% of awater-soluble organic detergent; (2) from 60% to 95% of awater-insoluble siliceous abrasive; (3) an alkaline detergency buildersalt; (4) an N-chloroimide bleaching agent; and (5) 2 to 15% sodiumacetate.

The preferred scouring cleanser compositions of the invention caninclude any of the water-soluble organic detergent compounds describedhereinbefore. The abrasive materials of the scouring cleansercompositions of the invention are well known in the art and includewaterinsoluble siliceous abrasive materials such as silica, feldspar,pumice, volcanic ash, diatomaceous earth, bentonite, talc and the like.Silica and feldspar are preferred abrasive materials from the standpointof their ready availability, cost, hardness and whiteness properties.The particle size, hardness and shape characteristics will varydepending upon the contemplated use of the scouring composition.Generally, the particle size of the scouring abrasive employed hereinranges in size from about 0.3 mm. diameter to about 0.001 mm. diameterand finer. Normally, at least about of the abrasive materials will passthrough a sieve having mesh openings of 0.074 mm. At least about 5% byweight of the abrasive material will remain on a sieve having meshopenings of 0.037 mm. The abrasive component comprises from 60% to 95 ofthe scouring cleanser compositions of the invention. Preferably, theabrasive material comprises from about 70% to about by weight of thecleanser.

Suitable detergency builder salts of the preferred scouring cleansercompositions of the invention include those specifically mentionedhereinbefore. Especially preferred, from the standpoint of makingpossible the formulation of detergent compositions free of phosphatecomponents, are the alkali metal carbonates, e.g., sodium and potassiumcarbonate. Especially preferred is sodium carbonate from the standpointsof providing desirable cleaning and building effects, cost andavailability. Any of the sources of carbonate knownin the detergent artscan be employed. Suitable carbonate sources include those available inthe art as soda ash, including the anhydrous calcined or hydrated formsalthough an anhydrous form is preferred from the standpoint of providingno mois ture. Sodium or potassium sesquicarbonate can also be employed.The bicarbonate portion of mixtures commonly known in the art assesquicarbonate, is believed to exist in the form of carbonate under thepH conditions of normal usage of the scouring compositions of theinvention in slurry form.

It is preferable, in the formulation of the preferred scouring cleansercompositions of the invention, to employ the alkali metal carbonate inan anhydrous form so as to permit the preparation of a free-flowing andrelatively non-agglomerating composition. The preferred anhydrousbuilder salts provide hydration capacity during formulation or storageof the compositions of the invention and permit the preparation ofcompositions which are dry to the touch and which are substantiallydevoid of uncombined moisture. The compositions of the inventionnormally contain from 0.1% to about 1% water upon manufacture,preferably less than 0.75% by weight. Thus, it is preferred that thewater-soluble alkali metal carbonate detergency builder component of thecompositions of the invention be present in a hydratable form.

The preferred carbonate, built abrasive scouring cleanser compositionsof the invention, will contain for aluminum-mark-removing purposes,calcium oxide, calcium hydroxide or a mixture thereof, in a Weight ratioof the calcium compound to the carbonate builder of from 0.01:1 to 04:1.Such compositions are effective in removing aluminum smears fromporcelain surfaces such as those which are deposited on porcelain sinksurfaces by contact with aluminum pots, pans and utensils incident tonormal household cleansing and scouring operations.

An especially preferred abrasive scouring cleanser composition of theinvention consists essentially of:

(1) from about 1% to about 4% of a compatible watersoluble organicdetergent,

(2) from 8% to 14% of sodium carbonate;

(3) from to 2% calcium oxide or hydroxide;

(4) from 70% to about 90% of a siliceous abrasive material;

(5 from 0.2% to 1% of an alkali metal dichlorocyanurate; and

(6) from 2% to sodium acetate.

(7) from 0.1 to 5% moisture.

In order to maintain the substantially dry form of the compositions ofthe invention, it is desirable that these compositions be packaged inmoisture-impermeable materials, e.g., plastic, glass, metal, fiber canswith interior Wax coating or metal foil.

The following Examples are illustrative of the present invention and itwill be understood that the invention is not limited thereto. All partsand percentages are by weight unless otherwise specified.

EXAMPLE I In all of the Examples herein, the silca and sodium alkylbenzene sulfonate components had the following descriptions, except asnoted:

The silica abrasive contained about 99.6 parts silica, approximately 0.2parts moisture, 0.2 sodium sulfate and about 0.03 parts pigment. Theparticle size varied from about 5 microns to about 50 microns with themajor portion of the particles being in the range from 10 microns toabout 20 microns.

The sodium alkyl benzene sulfonate had a distribution of C to C alkylchains and an average of C In Examples I to III, the sodium alkylbenzene sulfonate was prepared into a premix with the sodium carbonateby spraying 3.7 parts of an anqeous slurry (60% sodium alkyl benzenesulfonate; 1.5% sodium sulfate; 0.5% sodium xylene benzene sulfonate;38% water) onto 12.5 parts of anhydrous sodium carbonate and drying theresulting mixture to about 1% water, including water of hydration. Theresulting agglomerate was ground to provide a distribution of particlesizes permitting admixture with the remaining components.

An abrasive scouring cleanser composition was prepared by dry mixing:

Composition Component B C D E In order to determine the stability of theaboveidentified compositions (A through E) against loss of chlorine uponstanding, each of the compositions were subjected to ageing treatmentemploying a temperature of F. and a relative humidity of 80. Sampleswere stored in corrugated cardboard cylinders having metallic tops withholes punched for removal of the sample from the container. Samples werestored with the holes covered (sealed) with tape and with the taperemoved (opened). Measurements to determine chlorine content were takenat the intervals specified in the following table. Determinations ofavailable chlorine content were made employing a standardizedthiosulfate titration method. In accordance with this method, the sampleis dissolved in Water, and excess of potassium iodide is added andacetic acid is added to liberate iodine. The solution is titrated withsodium thiosulfate to a clear endpoint. The results are presented asfollows:

TABLE I Stability at 80 F./80% R.H.

Composition A B C D E Time Percent available chlorine (scaled/open)Initial 59 59 .59 59 1 Week. 55/.30 .58/. 58 .59/. 58 .55/.54 .59/.57 2weeks... 54/. 15 .54/14 58/. 57 51/. 39 .58/.52 3 weeks. 43/1 54/.1655/. 37 54/.16 58/.43 4 weeks" 44/1 56/1 56/. 20 53/1 56/. 20 5 weeks 41.55 .56 .51 .55

NOTE.T =trace.

9 deterioration within three weeks. Comparison of compositions B and Cand D and B shows the relative advantage of 5% sodium acetate over 3%.

EXAMPLE II Abrasive scouring cleanser compositions were prepared by drymixing:

Composition Component Sodium carbonate/sodium alkyl benzene sulfonatepremix (125 parts sodium carbonate, anhydrous basis; 2.2 parts sodiumbenzene sulfonate; 0.3 parts Water, sodium xylene sulfonate and sodiumsulfa 15 15 Potassium dichlorocyanuratefi 1. 1.0 Sodium acetate 10.0Lime (58% calcium hydroxide; 42% magnesium oxide) 1.1 1.1 Perfume 0. 150. l5 Silica/sodium sulfamate premix 82. 9 72. 9 pH 12.0 11.85

Compositions F and G were evaluated for available chlorine using themethod described hereinbefore. Storage was at 80 F. and 80% relativehumidity both sealed and open. The results obtained are reported asfollows:

TABLE II Stability at 80 F./80% R.H.

Composition Percent available chlorine (sealed/open) 6 months Abrasivescouring compositions were prepared by admixing:

Composition N I J K Component Parts by weight Sodium carbonate/sodiumalkyl benzene sulfonate premix (12.5 parts sodium carbonate,

anhydrous basis; 2.2 parts sodium benzene sulfonate; 0.3 parts Water,sodium xylene sulfonate and sodium sulfate) 15 15 15 15 Potassiumdichlorocyanuratelsodium sulfate Potassium diehlorocyanurate 0 Sodiumacetate 3.0 Lime (58% calcium hydroxide; 42% magnesium oxide) 1.1 1.11.1 1.1 Perfume 0.15 0. 15 0.15 0. 15 Silica/sodium sulfamate premixBalance to 100 Compositions H through K were evaluated for availablechlorine content in the manner described in Ex- Parts by weight 1O ampleI after storage at /80% R.H. The results are tabulated as follows:

Abrasive scouring compositions were prepared by dry mixing:

Component Sodium carbonate/sodium alkyl benzene sulfonatei sodiumacetate premix (12.5 parts sodium carbonate, anhydrous basis; 2.2 partssodium benzene sulfonate; 0.3 parts water, sodium xylene sulfonate andsodium sulfate; 3 parts sodium acetate Sodium carbonate/sodium alkylbenzene sulfonate premix (12.5 parts sodium carbonate, anhydrous basis;2.2 parts sodium benzene sulfonate; 0.3

parts water, sodium xylene sulfonate and sodium sulfate) Sodium acetate,anhydrous. Potassium diohlorocyanurate/sodium s o x 1.1 1.1Silica/sodium suliamate prem Balance to Compositions L and M wereevaluated for available chlorine after storage at (1) 80 F. and 80relative humidity and (2) 80 F. and ambient humidity, The results aretabulated as follows:

- TABLE IV Stability at 80 F./80% RH.

Composition Time Percent available chlorine (sealed/open) Initial 56 5655/. 28 53/. 46 54/1 53/. 36 51/T 43/1 44/1 53/[ 12 weeks 38/0 51/0NOTE.T =trace.

TABLE V Stability at 80 F./ambient R.H.

Composition Time Percent available chlorine (sealed/open) Initial 56 561 week 56/. 56 56/. 51 2 weeks 5 5/. 56 53/. 52 4 weeks 53/. 53 52/. 518 weeks 53/. 53 50/. 27 12 weeks 51]. 54 50/. 52

As is apparent from the above data, Composition M exhibits desirablestability. Composition L, while it withstood storage at 80 F./ambienthumidity, deteriorated substantially relative to Composition M at themore severe storage conditions of 80 F. and 80% relative humidity.

EXAMPLE V Four abrasive scouring compositions (Compositions N through Q)were evaluated for their filming characteristics in the followingmanner. Slurries (50% by weight in water) were applied to a blackceramic tile by passing the slurry across the tile with the aid of aterry cloth. Two samples were applied side by side on a single tile.Following application of the cleanser samples, the bottom half of eachtile was rinsed so as to provide quadrant areas permitting evaluation offilming characteristics for each sample on both an unrinsed and rinsedbasis. The samples were visually graded by a panel of judges on around-robin paired-comparison basis with the grade of 1 indicating avery slight difference, 2 a slight difference, 3 a moderate differenceand 4 a large difierence. The four samples evaluated included acomposition corresponding to Composition A of Example I and compositionshaving, respectively 1%, 2% and 4% of sodium acetate, the amount ofsilica/ sodium sulfamate premix being reduced by the amount of sodiumacetate present.

The following filming grades (unrinsed comparisons) were obtained.

Composition N (no sodium acetate) 2 Composition (1% sodium acetate) 1Composition P (2% sodium acetate) +1.25 Composition Q (4% sodiumacetate) +1.75

As is apparent from the above data, there was a diflerence between theControl (N) and 4% sodium acetatecontaining Composition (Q) of greaterthan 3 units.

A subsequent evaluation of compositions corresponding to Compositions Nand Q showed a +1.75 advantage for Q over N on an unrinsed basis.Another evaluation showed a +2 advantage for Q over N on an unrinsedbasis.

EXAMPLE VI A detergent composition suited for automatic dishwashingcomprises by weight the following:

EXAMPLE VII A detergent bleach composition adapated for the removal ofstains on enamel sinks, tarnish stains on metal ware and for bleachingtextiles comprises the following in parts by weight:

1,3-dichloro-5,5-dimethylhyrantoin Wetting agents (sodium isopropylnaphthalene sulfonate) 6 Anhydrous tetrasodium pyrophosphate 24 Sodiumdodecyl benzene sulfonate 3 Anhydrous borax 15 Sodium sulfate 33 Sodiumacetate 4 EXAMPLE VIII An abrasive scouring cleanser providing ahypobromite oxidizing species in solution is prepared by mixingintimately the following dry constituents:

Parts by Weight Silica (at least 80% by weight passing through a wiresieve in which the openings between the wires are 0.074 mm.) 75 Sodiumcarbonate, anhydrous 10 Sodium dodecyl benzene sulfonate 3Trichlorocyanuric acid 2 Sodium bromide 2 Sodium acetate, anhydrous 8What is claimed is: 1. A detergent composition stabilized against lossof available halogen consisting essentially of from about 0.1% to 60% byweight of a water-soluble organic detergent selected from the groupconsisting of soap, nonsoap anionic, nonionic, zwitterionic and cationicdetergents; from about 0.1% to 95 by weight of a heterocyclicN-halo-imide bleaching agent having from 4 to about 6 members in itsring structure with the halo moiety of said bleaching agent beingselected from the group consisting of chloro and bromo; free moisture;and anhydrous sodium acetate in an amount sufficient to provide a weightratio of acetate to free moisture of from about 0.421 to 150:1 and tothereby stabilize the N-halo-imide against loss of halogen.

2. The detergent composition of Claim 1 wherein the N-halo-imide isselected from the group consisting of dichloroisocyanuric acid, thealkali metal salts of dichloroisocyanuric acid and trichloroisocyanuricacid.

3. The detergent composition of Claim 2 wherein N- halo-irnide ispotassium dichloroisocyanurate.

4. The detergent composition of Claim 3 wherein the water-solubleorganic detergent is selected from the group consisting of water-solublesulfated and sulfonated anionic synthetic detergents.

5. A detergent composition stabilized against loss of chlorineconsisting essentially of from about 0.1% to 10% by weight of awater-soluble organic detergent selected from the group consisting ofsoap, non-soap anionic, nonionic, switterionic and cationic detergents;from about 60% to 95% by weight of a water-insoluble abrasive scouringagent having particle sizes of from about 0.3 millimeter to about 0.001millimeter; an alkaline inorganic builder salt; from about 0.1% to 25%by weight of a heterocyclic N-chloro-imide bleaching agent having from 4to about 6 members in its ring structure; free moisture; and anhydroussodium acetate in an amount sufiicient to provide a weight ratio ofacetate to free moisture of from about 0.421 to 150:1 and to therebystabilize the N-chloroimide against loss of chlorine.

6. The composition of Claim 5 wherein the waterinsoluble abrasivescouring agent is a siliceous abrasive selected from the groupconsisting of silica, feldspar, pumice, volcanic ash, diatomaceousearth, bentonite and talc.

7. The detergent composition of Claim 6 wherein the water-solubleorganic detergent is selected from the group consisting of water-solublesulfated and sulfonated anionic synthetic detergents and is present inan amount of from 1% to 4% by weight of the composition.

8. The detergent composition of Claim 7 wherein the N-halo-imide isselected from the group consisting of dichloroisocyanuric acid, thealkali metal salts of dichloro isocyanuric acid and trichloroisocyanuricacid.

9. The detergent composition of Claim 8 wherein the N-chloro-imide ispresent in an amount of from 0.2 to 1% of the composition.

10. The detergent composition of Claim 9 wherein the N-chloro-imide ispotassium dichloroisocyanurate.

11. The detergent composition of Claim 10 wherein the sodium acetate ispresent in an amount of from 2% to 15% of the composition.

12. A composition in accordance with Claim 11 wherein the alkalineinorganic builder salt is selected from the group consisting of sodiumcarbonate, potassium carbonate, sodium sesquicarbonate and potassiumsesquicarbonate and wherein said composition is free of phosphatecomponents.

13. A composition in accordance with Claim 12 wherein the alkalinebuilder salt is sodium carbonate and is present to the extent of from 8%to 14% by weight of the composition; wherein the siliceous abrasivematerial is present to the extent of from to about by weight of thecomposition; wherein the potassium dichloroisocyanurate is present tothe extent of from 0.2% to 1% by weight of the composition; wherein freemoisture is present to the extent of from 0.1% to 5% by weight of thecomposition and wherein the compositior i c ontains from 0% to 2% of2,993,745 7/1961 Doi s it 25295 X an aluminum mark removing agentselected from the 3,128,250 4/1964 Lintner 252-99 group consisting ofcalcium oxide and calcium hydroxide. FOREIGN PATENTS References Cited 5587,074 1/1959 Italy. UNITED STATES PATENTS MAYER WEINBLATI, PrimaryExaminer 3,575,865 4/1971 Burke et a1 25295 US. Cl. X.R.

3,715,314 2/1973 Morgenstern 252-95 25299, 187 C Disclaimer3,829,385.0hm"les Theodom'c Abbott, J7., and George Ounm'ngham Smith,JR, Montgomery, Ohio. DETERGENT COMPOSITIONS CONTAIN- INGN-CHLOROIMIDES. Patent dated Aug. 13, 1974. Disclaimer filed Sept. 12,1974, by the assignee, The Pwocter db Gamble Company.

Hereby disclaims the term of this patent subsequent to June 18, 1991.

[Ofiioial Gazette June 24, 1.975.]

Disclaimer 3,829,885.0harles Theodom'e Abbott, J9., and GeorgeOunningham Smith, J72,

Montgomery, Ohio. DETERGENT COMPOSITIONS CONTAIN ING N-CHLOROIMIDES.Patent dated Aug. 13, 1974. Disclaimer filed Sept. 12, 197 4, by theassignee, The Procter d Gamble Uompany.

Hereby disclaims the term of this patent subsequent to June 18, 1991.

[Ofii'ez'al Gazette June 24, 1975.]

